CN104037326A - Stacked organic light emitting device and preparation method - Google Patents
Stacked organic light emitting device and preparation method Download PDFInfo
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- CN104037326A CN104037326A CN201310070574.1A CN201310070574A CN104037326A CN 104037326 A CN104037326 A CN 104037326A CN 201310070574 A CN201310070574 A CN 201310070574A CN 104037326 A CN104037326 A CN 104037326A
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention discloses a stacked organic light emitting device comprising an anode, a hole injection layer, a first hole transport layer, a first light emitting layer, a first electron transport layer, a charge generation layer, a second hole transport layer, a second light emitting layer, a second electron transport layer, an electron injection layer and a cathode which are stacked sequentially. The charge generation layer comprises an n-type doped layer, a metal elemental doped layer and a metal oxide layer which are stacked sequentially. The n-type doped layer can improve the electron transport rate, formed nano particles have a scattering effect on light, and a metal elementary substance is added and doped to improve the conductivity of the n-type doped layer. The metal elemental doped layer is doped with low work function metal and high work function metal, which can improve the charge regeneration ability and stability of the device. The metal oxide layer can improve the hole regeneration and transport ability and can enhance transport of electrons in the charge generation layer. The invention further provides a preparation method of the stacked organic light emitting device.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of laminated organic electroluminescent device and preparation method thereof.
Background technology
1987, the C.W.Tang of Eastman Kodak company of the U.S. and VanSlyke reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).Under 10V, brightness reaches 1000cd/m
2, its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.At present, in order to improve luminosity and luminous efficiency, increasing research is taking laminated device as main, this structure is normally together in series several luminescence units as articulamentum with charge generation layer, compared with unit component, multilayer devices often has current efficiency and luminosity at double, at present research many be utilize two or more to have that hole is injected or material of electronic injection as charge generating layers (as Cs:BCP/V
2o
5), or N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq
3: Li) and p-type (NPB:FeCl
3)) or Al-WO
3-Au etc. are linked in sequence multiple luminescence units and form, but this device light transmission rate and luminous efficiency are all lower, are unfavorable for the further application of laminated organic electroluminescent device.In addition, this charge generation layer at least needs to carry out more than twice operation, brings certain complexity to preparation.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of laminated organic electroluminescent device, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually; Described N-shaped doped layer can improve electric transmission speed, and the nano particle forming has scattering process to light, add work function be the metal of 4.0～6.0eV as doping, can improve the conductivity of charge generation layer.The metal that the metal that metal simple-substance doped layer employing work function is 2.0～4.0eV and work function are 4.0～6.0eV adulterates, improve charge regeneration ability and the stability of device, and metal oxide layer can improve regeneration and the transmittability in hole, also can strengthen the transmission of electronics at charge generation layer; Meanwhile, the present invention also provides a kind of preparation method of above-mentioned laminated organic electroluminescent device, and the present invention prepares charge generation layer and only uses the method for evaporation to prepare, and method is simple.
First aspect, the invention provides a kind of laminated organic electroluminescent device, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually; The material of described N-shaped doped layer is that work function is the metal of 4.0～6.0eV and the composite material that N-shaped metal oxide forms for the ratio of 0.05:1～0.3:1 in mass ratio, and described N-shaped metal oxide is zinc oxide (ZnO) or titanium dioxide (TiO
2); Described metal simple-substance doped layer is that work function is the composite material that the metal of 2.0～4.0eV and metal that work function is 4.0～6.0eV form for 1:1～20:1 in mass ratio; Described metal oxide layer material is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
Preferably, described N-shaped doped layer thickness is 10～40nm.
Preferably, described metal simple-substance doped layer thickness is 1～20nm.
Preferably, described metal oxide layer thickness is 10～30nm.
Preferably, the metal that described work function is 2.0～4.0eV is magnesium (Mg), calcium (Ca) or ytterbium (Yb).
Preferably, the metal that described work function is 4.0～6.0eV is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
Preferably, described anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), more preferably ITO.
Preferably, described hole injection layer material is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5), thickness is 20～80nm;
More preferably, described hole injection layer material is V
2o
5, thickness is 40nm.
Preferably, described the first hole transmission layer and the second hole transmission layer material are 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the first hole transmission layer material is NPB, and thickness is 30nm, and the second hole transmission layer material is NPB, and thickness is 50nm.
Preferably, described the first luminescent layer and the second luminescent layer material are 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) or oxine aluminium (Alq
3), thickness is 5～40nm.
More preferably, described the first luminescent layer and the second luminescent layer material are ADN, and thickness is 10nm.
Preferably, described the first electron transfer layer and the second electron transfer layer material are 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or N-aryl benzimidazole (TPBI), thickness is 40～200nm.
More preferably, described the first electron transfer layer material is Bphen, and thickness is 180nm, and described the second electron transfer layer material is Bphen, and thickness is 80nm.
Preferably, described electron injecting layer material is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF), thickness is 0.5～10nm;
More preferably, described electron injecting layer material is LiF, and thickness is 1nm.
Preferably, described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and thickness is 60～300nm.
More preferably, described negative electrode is Ag, and thickness is 120nm.
The invention discloses a kind of laminated organic electroluminescent device, in this device, charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually, and described N-shaped doped layer is more close to described anode than metal oxide layer, described N-shaped doped layer material is the composite material that high-work-function metal (work function is 4.0～6.0eV) and N-shaped metal oxide form, although N-shaped metal oxide is semi-conducting material, but due to some defects (as room oxygen and interstitial atom) of itself, the electric conductivity of material is not fine, after particularly making thin-film material, owing to there being a large amount of crystal boundaries between material granule, the scattering of charge carrier on crystal boundary increases, make its conductivity be difficult to meet the requirement of conducting film performance, in order to improve conductivity, in N-shaped metal oxide, introduce high-work-function metal, so that transportable free electron to be provided, improve the concentration of charge carrier, the electric conductivity of enhanced film, and the particle in the thin-film material forming has scattering process to light, improve the luminous efficiency of device.Due to low workfunction metal unstable chemcial property, apt to deteriorate under water oxygen atmosphere, and then the stability of destruction device, metal simple-substance doped layer adopts low workfunction metal (work function is 2.0～4.0eV) and high-work-function metal (work function is 4.0～6.0eV) to adulterate, improve charge regeneration ability, also improved the stability of charge generation layer simultaneously; And metal oxide layer material is bipolarity metal oxide, can improve regeneration and the transmittability in hole, also can strengthen the transmission of electronics at charge generation layer, this laminated device can effectively improve luminous efficiency.
Second aspect, the invention provides a kind of preparation method of laminated organic electroluminescent device, comprises following operating procedure:
Required size anode is provided, dry after cleaning;
At described anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and charge generation layer; Described charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually; The material of described N-shaped doped layer is that work function is the metal of 4.0～6.0eV and the composite material that N-shaped metal oxide forms for the ratio of 0.05:1～0.3:1 in mass ratio, and described N-shaped metal oxide is ZnO or TiO
2; Described metal simple-substance doped layer is that work function is the composite material that the metal of 2.0～4.0eV and metal that work function is 4.0～6.0eV form for 1:1～20:1 in mass ratio; Described metal oxide layer material is MoO
3, WO
3or V
2o
5; The evaporation condition of described N-shaped doped layer, metal simple-substance doped layer and metal oxide layer is: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 1～10nm/s;
Evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on charge generation layer, finally obtain laminated organic electroluminescent device.
Preferably, described N-shaped doped layer thickness is 10～40nm.
Preferably, described metal simple-substance doped layer thickness is 1～20nm.
Preferably, described metal oxide layer thickness is 10～30nm.
Preferably, the metal that described work function is 2.0～4.0eV is Mg, Ca or Yb; Wherein, the work function of Mg is 3.6eV, and the work function of Ca is 2.9eV, and the work function of Yb is 2.6eV.
Preferably, the metal that described work function is 4.0～6.0eV is Ag, Al, Pt or Au; Wherein the work function of Ag is 4.6eV, and the work function of Al is 4.2eV, and the work function of Pt is 5.6eV, and the work function of Au is 5.4eV.
Preferably, the evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 1～10nm/s.
Preferably, described the first hole transmission layer, the first luminescent layer, the first electron transfer layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～1nm/s.
Preferably, described anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Preferably, described in the anode of required size is provided, concrete operations are: anode substrate is carried out to photoetching treatment, be then cut into needed size.
Preferably, anode is used successively liquid detergent by being operating as that described cleaning is dried afterwards, deionized water, and acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
Preferably, described hole injection layer material is molybdenum trioxide MoO
3, WO
3or V
2o
5, thickness is 20～80nm;
More preferably, hole injection layer material is V
2o
5, thickness is 40nm.
Preferably, the first described hole transmission layer is identical with the second hole transmission layer material, is TAPC, TCTA or NPB, and thickness is 20～60nm.
More preferably, the first hole transmission layer material is for being NPB, and thickness is 30nm, and the second hole transmission layer material is NPB, and thickness is 50nm.
Preferably, described the first luminescent layer and the second luminescent layer material are DCJTB, ADN, BCzVBi or Alq
3, thickness is 5～40nm.
More preferably, described the first luminescent layer and the second luminescent layer material are ADN, and thickness is 10nm.
Preferably, the first and second described electron transfer layer materials are identical, are Bphen, TAZ or TPBI, and thickness is 40～200nm.
More preferably, described the first electron transfer layer is Bphen, and thickness is 180nm, and described the second electron transfer layer is Bphen, and thickness is 80nm.
Preferably, described electron injecting layer material is Cs
2cO
3, CsF, CsN
3or LiF, thickness is 0.5～10nm;
More preferably, described electron injecting layer is preferably LiF, and thickness is 1nm.
Preferably, described negative electrode is Ag, Al, Pt or Au, and thickness is 60～300nm.
More preferably, described negative electrode is Ag, and thickness is 120nm.
Sky of the present invention has been opened a kind of laminated organic electroluminescent device, and in this device, charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually; Described N-shaped doped layer material is the composite material that high-work-function metal (work function is 4.0～6.0eV) and N-shaped metal oxide form, N-shaped doped layer can improve electric transmission speed, and the particle in the thin-film material that preparation forms has scattering process to light, improve the luminous efficiency of device, add high-work-function metal as doping, can improve the conductivity of charge generation layer.Metal simple-substance doped layer adopts low workfunction metal (work function is 2.0～4.0eV) and high-work-function metal (work function is 4.0～6.0eV) to adulterate, improve charge regeneration ability and the stability of device, and metal oxide layer material is bipolarity metal oxide, can improve regeneration and the transmittability in hole, also can strengthen the transmission of electronics at charge generation layer, this laminated device can effectively improve luminous efficiency.The present invention prepares charge generation layer and only uses the method for evaporation to prepare, and method is simple.
Brief description of the drawings
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in execution mode be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of the embodiment of the present invention 1 laminated organic electroluminescent device;
Fig. 2 is brightness and the luminous efficiency graph of a relation of the embodiment of the present invention 1 and comparative example's organic electroluminescence device.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment 1
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected ito glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is V
2o
5, thickness is 40nm, evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s; The first hole transmission layer material is NPB, and thickness is 30nm, and the material of the first luminescent layer is ADN, thickness is 10nm, the first electron transfer layer material is Bphen, and thickness is 180nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first on the first electron transfer layer, evaporating Al and ZnO are the composite material of the ratio formation of 0.12:1 in mass ratio, obtaining thickness is the N-shaped doped layer of 15nm, on N-shaped doped layer, evaporation Mg and Ag are the composite material of the ratio formation of 10:1 in mass ratio, obtaining thickness is 5nm metal simple-substance doped layer, evaporation MoO on metal simple-substance doped layer
3, obtaining the metal oxide layer that thickness is 15nm, the evaporation condition of N-shaped doped layer, metal simple-substance doped layer and metal oxide layer is: evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on metal oxide layer, the second hole transmission layer material is NPB, thickness is 50nm, the second electron transfer layer material is Bphen, thickness is 80nm, electron injecting layer material is LiF, and thickness is 1nm, and the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s; The material of negative electrode is Ag, and thickness is 100nm, and evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s.
Fig. 1 is the structural representation of the laminated organic electroluminescent device of the present embodiment.As shown in Figure 1, laminated organic electroluminescent device prepared by the present embodiment, comprise the anode 1, hole injection layer 2, the first hole transmission layer 3, the first luminescent layer 4, the first electron transfer layer 5, charge generation layer 6, the second hole transmission layer 7, the second luminescent layer 8, the second electron transfer layer 9, electron injecting layer 10 and the negative electrode 11 that stack gradually, charge generation layer comprises the N-shaped doped layer 61, metal simple-substance doped layer 62 and the metal oxide layer 63 that stack gradually.Concrete structure is expressed as:
Ito glass/V
2o
5/ NPB/ADN/Bphen/ZnO:Al/Mg:Ag/MoO
3/ NPB/ADN/Bphen/LiF/Ag, wherein, brace "/" represents layer structure, the colon ": " in ZnO:Al and Mg:Ag represents to mix, lower same.
Embodiment 2
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected AZO glass, first anode is carried out to photoetching treatment, is then cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is V
2o
5, thickness is 80nm, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s; The first hole transmission layer material is NPB, and thickness is 60nm, and the material of the first luminescent layer is ADN, thickness is 5nm, the first electron transfer layer material is TPBI, and thickness is 40nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporating Al and TiO on the first electron transfer layer
2be the composite material of the ratio formation of 0.3:1 in mass ratio, obtaining thickness is the N-shaped doped layer of 10nm, on N-shaped doped layer, evaporation Ca and Ag are the composite material of the ratio formation of 1:1 in mass ratio, and obtaining thickness is 1nm metal simple-substance doped layer, evaporation WO on metal simple-substance doped layer
3, obtaining the metal oxide layer that thickness is 30nm, the evaporation condition of N-shaped doped layer, metal simple-substance doped layer and metal oxide layer is: evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on metal oxide layer, the second hole transmission layer material is TAPC, thickness is 20nm, the second luminescent layer material is BCzVBi, thickness is 40nm, the second electron transfer layer material is TAZ, and thickness is 200nm, and electron injecting layer material is CsN
3, thickness is 0.5nm, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s; The material of negative electrode is Pt, and thickness is 60nm, and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually.Concrete structure is expressed as: AZO glass/V
2o
5/ NPB/ADN/TPBI/TiO
2: Al/Ca:Ag/WO
3/ TAPC/BCzVBi/TAZ/CsN
3/ Pt.
Embodiment 3
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected IZO glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is V
2o
5, thickness is 20nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s; The first hole transmission layer material is TAPC, and thickness is 30nm, and the material of the first luminescent layer is DCJTB, thickness is 10nm, the first electron transfer layer material is TAZ, and thickness is 200nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 1 × 10
-3pa, evaporation speed is 0.5nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation Pt and TiO on the first electron transfer layer
2be the composite material of the ratio formation of 0.05:1 in mass ratio, obtaining thickness is the N-shaped doped layer of 40nm, on N-shaped doped layer, evaporation Yb and Au are the composite material of the ratio formation of 20:1 in mass ratio, and obtaining thickness is the metal simple-substance doped layer of 20nm, evaporation V on metal simple-substance doped layer
2o
5, obtaining the metal oxide layer that thickness is 10nm, the evaporation condition of N-shaped doped layer, metal simple-substance doped layer and metal oxide layer is: evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on metal oxide layer, the second hole transmission layer material is TCTA, thickness is 60nm, the second luminescent layer material is DCJTB, thickness is 5nm, the second electron transfer layer material is Bphen, and thickness is 40nm, and electron injecting layer material is Cs
2cO
3, thickness is 10nm, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 1 × 10
-3pa, evaporation speed is 0.5nm/s; The material of negative electrode is Al, and thickness is 300nm, and evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually.Concrete structure is expressed as: IZO glass/V
2o
5/ TAPC/DCJTB/TAZ/TiO
2: Pt/Yb:Au/V
2o
5/ TCTA/DCJTB/Bphen/Cs
2cO
3/ Al.
Embodiment 4
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected IZO glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is MoO
3, thickness is 30nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s; The first hole transmission layer material is NPB, and thickness is 50nm, and the material of the first luminescent layer is Alq
3, thickness is 40nm, and the first electron transfer layer material is Bphen, and thickness is 40nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 1 × 10
-3pa, evaporation speed is 0.5nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first on the first electron transfer layer, evaporation Au and ZnO are the composite material of the ratio formation of 0.15:1 in mass ratio, obtaining thickness is the N-shaped doped layer of 12nm, on N-shaped doped layer, evaporation Mg and Pt are the composite material of the ratio formation of 5:1 in mass ratio, obtaining thickness is 15nm metal simple-substance doped layer, evaporation WO on metal simple-substance doped layer
3, obtaining the metal oxide layer that thickness is 18nm, the evaporation condition of N-shaped doped layer, metal simple-substance doped layer and metal oxide layer is: evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on metal oxide layer, the second hole transmission layer material is TAPC, and thickness is 50nm, and the second luminescent layer material is Alq
3, thickness is 35nm, the second electron transfer layer material is TPBI, thickness is 100nm, electron injecting layer material is CsF, and thickness is 2nm, and the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 1 × 10
-3pa, evaporation speed is 1nm/s; The material of negative electrode is Au, and thickness is 180nm, and evaporation pressure is 1 × 10
-3pa, evaporation speed is 10nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually.Concrete structure is expressed as: IZO glass/MoO
3/ NPB/Alq
3/ Bphen/ZnO:Au/Mg:Pt/WO
3/ TAPC/Alq
3/ TPBI/CsF/Au.
Comparative example
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, comparative example is existing organic electroluminescence device, comprise the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, the concrete structure of comparative example's organic electroluminescence device is: ito glass/V
2o
5/ NPB/ADN/Bphen/LiF/Ag, the thickness of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode is respectively: 40nm, 30nm, 10nm, 180nm, 1nm and 120nm.
Effect embodiment
Adopt fiber spectrometer (marine optics Ocean Optics company of the U.S., model: USB4000), current-voltage tester (Keithly company of the U.S., 2400), colorimeter (Japanese Konica Minolta company model:, model: CS-100A) test organic electroluminescence device brightness with luminous efficiency change curve, to investigate the luminous efficiency of device, tested object is embodiment 1 and comparative example's organic electroluminescence device.Test result as shown in Figure 2.Fig. 2 is the embodiment of the present invention 1 and the brightness of comparative example's organic electroluminescence device and the graph of a relation of luminous efficiency.
From Fig. 2, can find out, under different brightness, all large than comparative example of the luminous efficiency of embodiment 1, maximum luminous efficiency is 12.5lm/W, and that comparative example is only 6.7lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer in a kind of laminated organic electroluminescent device provided by the invention has effectively improved charge generation ability, has light scattering effect simultaneously, has effectively improved the luminous efficiency of device.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a laminated organic electroluminescent device, it is characterized in that, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually; The material of described N-shaped doped layer is that work function is the metal of 4.0～6.0eV and the composite material that N-shaped metal oxide forms for the ratio of 0.05:1～0.3:1 in mass ratio, and described N-shaped metal oxide is zinc oxide or titanium dioxide; Described metal simple-substance doped layer is that work function is the composite material that the metal of 2.0～4.0eV and metal that work function is 4.0～6.0eV form for 1:1～20:1 in mass ratio; Described metal oxide layer material is molybdenum trioxide, tungstic acid or vanadic oxide.
2. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described N-shaped doped layer thickness is 10～40nm; Described metal simple-substance doped layer thickness is 1～20nm; Described metal oxide layer thickness is 10～30nm.
3. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the metal that described work function is 2.0～4.0eV is magnesium, calcium or ytterbium.
4. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the metal that described work function is 4.0～6.0eV is silver, aluminium, platinum or gold.
5. a preparation method for laminated organic electroluminescent device, is characterized in that, comprises following operating procedure:
Required size anode is provided, dry after cleaning;
At described anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and charge generation layer; Described charge generation layer comprises the N-shaped doped layer, metal simple-substance doped layer and the metal oxide layer that stack gradually; The material of described N-shaped doped layer is that work function is the metal of 4.0～6.0eV and the composite material that N-shaped metal oxide forms for the ratio of 0.05:1～0.3:1 in mass ratio, and described N-shaped metal oxide is zinc oxide or titanium dioxide; Described metal simple-substance doped layer is that work function is the composite material that the metal of 2.0～4.0eV and metal that work function is 4.0～6.0eV form for 1:1～20:1 in mass ratio; Described metal oxide layer material is molybdenum trioxide, tungstic acid or vanadic oxide; The evaporation condition of described N-shaped doped layer, metal simple-substance doped layer and metal oxide layer is: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 1～10nm/s;
Evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on charge generation layer, finally obtain laminated organic electroluminescent device.
6. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, described N-shaped doped layer thickness is 10～40nm, and described metal simple-substance doped layer thickness is 1～20nm; Described metal oxide layer thickness is 10～30nm.
7. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the metal that described work function is 2.0～4.0eV is magnesium, calcium or ytterbium.
8. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the metal that described work function is 4.0～6.0eV is silver, aluminium, platinum or gold.
9. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 1～10nm/s.
10. the preparation method of laminated organic electroluminescent device as claimed in claim 5, it is characterized in that, described the first hole transmission layer, the first luminescent layer, the first electron transfer layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～1nm/s.
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| CN112331788A (en) * | 2019-12-30 | 2021-02-05 | 广东聚华印刷显示技术有限公司 | Light emitting device and method of manufacturing the same |
| CN117025018A (en) * | 2022-08-16 | 2023-11-10 | 广东聚华印刷显示技术有限公司 | Ink, and laminated light-emitting device and display device including the same |
| WO2024125109A1 (en) * | 2022-12-14 | 2024-06-20 | Tcl科技集团股份有限公司 | Light-emitting device and preparation method therefor, and display apparatus |
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